Linear polyester fiber dyed with water-insoluble azo dyestuffs



United States Patent Office 3,547,571 Patented Dec. 15, 1970 3,547,571LINEAR POLYESTER FIBER DYED WITH WATER-INSOLUBLE AZO DYESTUFFS HansjoergAngliker, Basel, Switzerland, assignor to Ciba Limited, Basel,Switzerland, a company of Switzerland No Drawing. Continuation-impart ofapplication Ser. No.

603,135, Dec. 20, 1966. This application Feb. 5, 1969,

Ser. No. 796,883 Claims priority, application Switzerland, Dec. 24,1965,

17,811/65; Oct. 28, 1966, 15,710/66 Int. Cl. D06p 1/18 US. Cl. 8-41Claims ABSTRACT OF THE DISCLOSURE Polyester fiber dyed with aWater-insoluble azo dyestutf of the formula in which A represents thenon-fiber-reactive radical of an aromatic or heterocyclic diazocomponent, X represents an oxygen or a sulphur atom or a direct bond, Rrepresents a cycloalkyl, aryl or aralkyl residue, R represents ahydrogen atom, an alkyl or alkoxy group or the residue XRI- Thisapplication is a continuation-in-part of application Ser. No. 603,135,filed Dec. 20, 1966; still pending.

The present invention is based on the observation that valuablewater-insoluble azo dyestuffs of the formula in which A represents theresidue of an aromatic or heterocyclic diazo component, X represents anoxygen or a sulphur atom or a direct bond, R represents a cycloalkyl,aryl or aralkyl residue, R represents a hydrogen atom, an alkyl oralkoxy group or the residue XR R represents a hydrogen atom or an alkylgroup that may be substituted, R represents a hydrogen atom or acyanoalkyl, acyloxyalkyl, carbalkoxyalkyl or cyanoalkoxyalkyl group, andin which either R must represent an alkyl, alkoxy or phenoxy, group inortho-position to the amino group or X must represent a sulphur atom ora direct bond when both R and R represent hydrogen atoms, may beobtained when a diazo compound of an aromatic or heterocyclic amine iscoupled with an amine of the formula Preferred diazo components areaminobenzenes, especially those of the formula in which Y represents ahydrogen or halogen atom or an alkyl, alkoxy, nitro, cyano, carbalkoxyor alkylsulphone group and Z represents a hydrogen or halogen atom or analkyl, cyano or trifluoromethyl group.

The following may be mentioned as examples:

aminobenzene,

1-amino-4-chlorobenzene, 1-amino-4-bromobenzene,1-amino-4-methylbenzene, 1-amino-4-nitrobenzene, 1-amino-4-cyanobenzene,1-amino-2,S-dicyanobenzene, 1-amino-4-methylsulphonylbenzene,1-amino-4-carbalkoxybenzene, 1-amino-2,4-dichlorobenzene,l-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene,1-amino-2-trifiuoromethyl-4-chlorobenzene,1-amino-2-cyano-4-chlorobenzene, l-amino-2-carbomethoxy-4-chlorobenzene,1amino-2-carbomethoxy-4-nitrobenzene, 1-amino-2-chloro-4-cyanobenzene,1-arnino-2-chloro-4-nitrobenzene, 1-amino-2-chloro-4-carbethoxybenzene,1-amin0-2-chloro-4-methylsulphonylbenzene,1-arnino-2-methylsulphonyl-4-chlorobenzene,1-amino-2-methylsulphonyl-4-nitrobenzene, l-amino-2,4-dinitrobenzene,1-amino-2,4-dicyanobenzene, 1-amino-2-cyano-4-methylsulphouylbenzene,1-amino-2,6-dichloro-4-cyanobenzene,1-amino-2,6-dichloro-4-nitrobenzene,1-amino-2,4-dicyano-6-chlorobenzene, 1-amino-2,4-dinitro-6-chlorobenzeneand especially 1-amino-2-cyano-4-nitrobenzene.

The following amines may be mentioned as members of the series ofheterocyclic diazo components:

Z-aminothiazole, Z-arnino-S-cyanothiazole,2-amino-4-rnethyl-5-nitrothiazole, 2-amini-4-methylthiazole,Z-amino-4-phenylthiazole,

2-amino-4- (4-chloro) -phenylthiazole, 2-amino-4- (4-nitro-phenylthiazole, 2-amino-6-chlorobenzthiazole,2-amino-6-methylsulphonylbenzthiazole, Z-amino-6-nitrobenzthiazole,2-amino-l,3,4-thiadiazole and Z-amino-1,3,5-thiadiazole.

The coupling components to be used in the process of the inventionpreferably correspond to the formula l O-rmornornorr in which Rrepresents an alkyl or alkoxy group, R7 rep resents a hydrogen atom, analkyl or alkoxy group, X represents an oxygen or a sulphur atom or amethylene group, X represents an oxygen or a sulphur atom, a methylenegroup or a direct bond and Y and Z each represents a hydrogen or halogenatom or an alkyl or alkoxy group.

Likewise of interest are coupling components of the formula in which Rrepresents an alkyl or alkoxy group, and X Y and Z have the meaningsgiven above. The said coupling components may be obtained by knownmethods, for example, by nitration of para-methoxy-diphenylether andsubsequent reduction. Examples are 3-phenoxyaniline,2-methoxy-S-phenoxyaniline, 2-methyl-S-phenoxyaniline,N-methyl-Z-methoxy-S-phenoxyaniline,N,N-dimethyl-2-methoxy-S-phenoxyaniline,N-ethyl-2-methoxy-S-phenoxyaniline, N,N-diethyl-2-methoxy-5-phenoxyaniline, N-cyanoethyl-3-phenoxyaniline,N-cyanoethyl-Z-methoxy-5-phenoxyaniline,N-cyanoethyl-2-ethoxy-5-phenoxyaniline,N-ethyl-N-cyanoethyl-2-methoxy-5-phenoxyaniline,N,N-di-cyanoethoxyethyl-Z-methoxy-5 -phenoxyaniline,N,N-di-acetoxyethyl-3 -phenoxyaniline,N,N-di-acetoxyethyl-Z-methoxy-S-phenoxyaniline,N-cyanoethyl-N-acetoxyethyl-Z-methoxy-5-phenoxyaniline,N,N-diethyl-S-phenoxyaniline, N ,N-diethyl-2-methyl-5-phenoxyaniline,N,N-diethyl-2-methoxy-5 para-chlorophenoxy -aniline,N,N-diethyl-2-methoxy-5- (meta-chlorophenoxy -aniline,N,N-diethyl-2-methoxy-5- para-methylphenoxy -aniline,N,N-diethyl-2-meth0xy-5- (meta-methylphenoxy -aniline,3-phenylmercaptoaniline, N,N-diethyl-2-methoxy-5 -phenylmercaptoaniline,N-cyanoethyl-3-phenylmercaptoaniline, N-ethyl-N-cyanoethyl-Z-methoxy-5-phenylmercaptoaniline, N-cyanoethyl-2-methoxy-S-phenylmercaptoaniline,N-ethyl-N-acetoxyethyl-2-methoxy-S-phenylmercaptoaniline,N-cyanoethyl-3-benzylmercaptoaniline, 3-phenylaniline,2-methoxy-5-phenylaniline, N-cyanoethyl-3-phenylaniline,N-cyanoethyl-Z-methoxy-S-phenylaniline, N,N-di-acetoxy-3-phenylaniline,N,N-di-acetoxy-Z-methoxy-5-phenylaniline, 3-benzylaniline,2-benzyloxyaniline, N-cyanoethyl-3-benzylaniline,N-cyanoethyl-2-benzylaniline, N-cyanoethyl-2-methoxy-S-benzylaniline,N-fi-cyanoethyl-2-benzyloxyaniline, N,N-di-acetoxy-3-benzylaniline,N,N--di-acetoxy-Z-methoxy-3-benzylaniline,N-bis-fi-acetoxyethyl-3-benzyloxyaniline andN-[i-cyanoethyl-2-phenylaniline.

Diazotization of the diazo components can be carried out by knownmethods, for example, with the aid of a mineral acid, especiallyhydrochloric acid, and sodium 4 nitrite, or, for example, with asolution of nitrosyl sulphuric acid in concentrated sulphuric acid.

Coupling can likewise be effected in known manner, for example, in aneutral to acid medium, if necessary, in the presence of sodium acetateor some similar buffer or catalyst which influences the rate ofcoupling, for example, pyridine or the salts thereof.

Subsequent to the coupling reaction, the dyestuffs formed can easily beisolated from the coupling mixture, for example, by filtration, becausethey are virtually insoluble in water.

The new dyestuffs are eminently suitable for dyeing and printingmaterials, especialy fibers and fabrics made, for example, fromcellulose triacetate and polyamides, but especially from aromaticpolyesters. They produce strong dyeings and prints possessing excellentproperties of fastness, especially fastness to light, sublimation andrubbing.

For dyeing, the new dyestuffs are advantageously used in a state of finedivision and dyeing is carried out in the presence of dispersing agents,for example, soap, sulphite cellulose waste liquor or syntheticdetergents, or a combination of different wetting and dispersing agents.Prior to dyeing, it is generally advantageous to convert the dyestuffinto a dyeing preparation containing a dispersing agent and the finelydivided dyestuff in a form such that a fine dispersion is obtained whenthe preparation is diluted with water. Dyestuff preparations of thiskind may be obtained in known manner, for example, by reprecipitation ofthe dyestuff from sulphuric acid and grinding the suspension so obtainedwith sulphite cellulose waste liquor, or, if necessary, by grinding thedyestuff in a highly efficient grinding apparatus in the dry or wetstate in the presence or absence of dispersing agent.

In order to produce stronger dyeings on polyethylene terephthalatefibers, it has been found to be advantageous to add a swelling agent tothe dyebath, or in particular, to carry out the dyeing process undersuperatmospheric pressure at a temperature above C., for example, at C.Suitable swelling agents are aromatic carboxylic acids, for example,benzoic or salicylic acid, phenols, for example, orthoorpara-hydroxydiphenyl, aromatic halogenated compounds, for example,chlorobenzene, ortho dichlorobenzene or trichlorobenzene,phenylmethylcarbinol or diphenyl. When dyeing under superatmosphericpressure, it has been found to be advantageous to render the dyebathslightly acid, for example, by the addition of a weak acid, for example,acetic acid.

By virtue of their fastness to alkali, the new dyestuffs are alsosuitable for application by the so-called thermofixation process inwhich the fabric to be dyed is impregnated, preferably at a temperaturenot exceeding 60 C., with an aqueous dispersion of the dyestuff, whichadvantageously contains 1 to 50% of urea and a thickening agent,especially sodium alginate, and then squeezed in the usual manner. It isexpedient to squeeze the impregnated material so that it retains 50 to100% of its dry weight of dye-liquor.

To the dyestuff, the material thus impregnated is heated to atemperature above 100 C., for example, to a temperature between and 220C., advantageously after a drying operation, for example, in a currentof warm air.

The above-mentioned thermofixation process is specially suitable for thedyeing of union fabrics made from a mixture of polyester and cellulosicfibers, especially cotton. In this case, in addition to the dyestuffs ofthe invention, the padding liquor should containdyestuffs suitable fordyeing cotton, especially vat dyestuffs or reactive dyestuffs, that isto say, dyestuffs which are fixed on cellulosic fibers by formation of achemical bond, for example, dyestuffs containing a chlorotriazine orchlorodiazine residue. In the last-mentioned case, it has been found tobe advantageous to add an agent capable of binding acid to the paddingsolution, for example, an alkali metal carbonate or phosphate, or aalkali metal borate or perborate, or mixtures thereof. When using vatdyestuffs, the padded fabric has to be treated subsequent to the heattreatment with an aqueous alkaline solution of one of the reducingagents commonly used in vat dyeing. Cotton fibers present in unionmaterial are left virtually unstained by the new dyestuffs because oftheir capacity to reserve cotton.

Because they reserve well on wool, the dyestufls of the invention arealso eminently suitable for dyeing union fabrics made from a mixture ofpolyester fibers and wool.

The dyeing obtained are advantageously subjected to an after-treatment,for example, by heating with an aqueous solution of a non-ionicdetergent.

The dyestuffs of the invention can also be applied by printingprocesses. In this method of application, a printing paste is used whichcontains, for example, the finely divided dyestufi together with theusual printing adjuvants, for example, wetting and thickening agents, ifnecessary, in admixture with one of the above-mentioned cottondyestuffs, together with urea and/or an agent capable of binding acid ifrequired.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by Weight.

EXAMPLE 1 2.9 parts of 2-chloro-4-nitraniline are suspended in 30 partsof water and 6 parts of concentrated hydrochloric acid are added. Aftercooling to C., 10 parts of 2 N sodium nitrite solution are addeddropwise. Subsequently, the batch is stirred for one hour, the excessnitrite is destroyed and then a solution of 4.5 parts ofN-fi-cyanoethyl-Z-methoxy-S-phenoxyaniline in 100 parts of glacialacetic acid is added, the temperature being kept below C. Finally, thedyestufl? is completely precipitated at the same temperature bybuflering with 30% sodium hydroxide solution. It dyes polyester fibersred tints possessing an excellent fastness to light and sublimation.

Dyeing prescription 1 part of the dyestuff obtained in the mannerdescribed in Example 1 is ground wet with 2 parts of a 50% aqueoussolution of the sodium salt of dinaphthylmethane disulphonic acid anddried.

The dyestuff preparation so obtained is mixed with 40- parts of aaqueous solution sodium N-benzyl-nheptadecyl-benzimidazol-disulfonateand then 4 parts of a 40% acetic acid solution are added. A dyebath of4,000 parts is prepared by dilution with water.

100 parts of cleansed polyester fiber material are entered into thedyebath so prepared at 50 C., the temperature is then raised to 120 to130 C. in half an hour, and dyeing is carried out for one hour at thattemperature in a closed vessel. The material is then well rinsed. Astrong red dyeing possessing an excellent fastness to light andsublimation is obtained.

EXAMPLE 2 A dyestuff which dyes polyester fibers orange tints possessingan excellent fastness to light and to sublimation is obtained when the4.5 parts of N-B-cyanoethyl-Z- methoxy-S-phenoxyaniline used in Example1 are replaced by 4 parts of N-fl-cyanoethyl-3-phenoxyaniline.

EXAMPLE 3 2.7 parts of 2-cyano-4-nitraniline are added in portions to 23parts of monohydrate in which 1.15 parts of sodium nitrite have beendissolved. The excess nitrite is destroyed and the diazo solution isadded dropwise at a temperature not exceeding 10 C. to a solution of 4.5parts of N-ficyanoethyl-Z-methoxy-5-phenoxyaniline in 100 parts of 80%acetic acid. After stirring for a short time, the dyestuff is completelyprecipitated at the same temperature by buffering with 30% sodiumhydroxide solution. It dyes polyester fibers ruby tints possessing anexcellent fastness to light and sublimation.

6 EXAMPLE 4 I II III 1 2-cyan04-nitro- N-bis-;3-acetoxyethyl-2-methoxy-5- Violet.

aniline. phenoxyaniline. 2 d0 N-bis-(cyanoethoxyethyD- Ruby.

2methoxy-5 phenoxyaniline. 3 ..do N-B-cyan0ethyl-N-B-acetoxyethyl-Claret.

5-methoxy-5-phenoxyaniline. N-fl-cyanoethyl-3-phenoxyaniline. Red.

5 .do N -bis-fl-acetoxyethyl-3 Claret.

phenoxyaniline.

6 ..do N-fl-cyanoethyl-3-(paramethyl- Red.

phenoxy)-aniline.

7 .do N-fi-eyanoethyl-3-(0rtho- Red.

chlor0phenoxy)-anili.ne.

8 do N -bis-fl-acetoxyethyl2-rnethoxy- Violet.

fi-phenylmercaptoaniline.

9 .do N -B-cyanoethyl-2-meth0xy-5- Claret.

(para-methylphenoxy)-aniline.

10 do N -fl cyanoethyl-2phcnoxyaniline.. Red.

11 do N-B-cyanoethyl-Z-methoxy-5- Claret. phenylaniline.

12 do N-B-carbethoxyethyl-Z-methoxy- Violet.

5-phenoxyaniline.

13 ..do N-fl-acetoxyethyl-Z-methoxy-S- Do.

phenoxyaniline.

14 do Di-N-ethylcarbamic acid ester D0.

of N -bis-B-hydr0xyethyl-2- methoxy-5-phenoxyaniline.

15 d0 N B-cyanoethyl-2-benzylaniline- Scarlet.

16. .do N'bisB-acetoxyethyl-3-benzyl- Ruby.

aniline.

17 do N fi-cyan0ethyl-2-benzyloxy- Red.

aniline.

18. 2-cyano4-nitro- N -bisacetoxypropyl-2- Violet.

aniline. methoxy-5-phenoxyaniline.

l9. 2, 6- dichloro4- N-B-cyanoethyl-2-methoxy-5- Brown.

mtraniline. phenoxyaniline.

20 ..do N-B-cyanoethyl-3-phenoxy- Orange.

aniline.

21.. 2-cyano4-nitro- N -bis-fl-acetoxyethyl-2-methoxy- Violet.

fi-bromaniline. G-phenoxyaniline.

22 do N-B-cyanoethyl-2-methoxy-5- Do.

phenoxyaniline.

23 ..do N -B-cyanoethyl-3-phenoxy- Reddish aniline. brown.

24-. 2-cyano-4-nitro-6- N 3-cyanoethyl-2-methoxy-5- Violet.

chloraniline. phenoxyaniline.

25. Z-methylsuldo Ruby.

phonylinitraniline.

26. 2-eyano-4-nitro- N B-cyan0ethyl-2, 5-diphenoxy- Do.

aniline. aniline.

27 .do Di-propionic acid ester of N -bis- Violet.

B-hydroxyethyl-2-methoxy-5- phenoxyaniline.

28. 2-amino-6-methyl- N-fi-cyanoethyl-2-methoxy-5- Red.

sulphonylphenoxyaniline. benzthiazole.

29. 2-cyano4-nitro- N-B-cyanoethyl-3-benzyl- Red.

aniline. mercaptoaniline.

30 .do N-B-cyanethyl-2-methoxy-5- Violet.

cyclohexylaniline.

31 d0 N -bis-B-acetoxyethyl-2-methoxy- Do.

5-cyclohexylani1ine.

EXAMPLE 5 2.7 parts of 2-cyano-4-nitraniline are introduced in portionsinto 23 parts of monohydrate in which 1.15 parts of sodium nitrite havebeen dissolved. The excess nitrite is destroyed and the diazo componentis added dropwise to a solution of 3.9 parts of4-methyl-3-amino-4-methoxydiphenylether in 200 parts of acetic acid, thetemperat'ure being kept at between 0 and 10 C. The pH value is kept atabout 4 by the simultaneous addition of 30% NaOH. After coupling, thedyestuff is isolated by filtration, washed with water and dried invacuo. It dyes polyester fibers violet tints.

The following table lists further components from which dyestuffs may beobtained when the diazo components listed in column I are coupled withthe coupling components indicated in column II. The tint produced onpolyester fibers is shown in column III.

I II III 1 2-cyauo-4nitro-aniline 2metl1oxy-fi-phenoxyaniline; Ruby.

2-methoxy-5-phenylaniline Violet. 2-methyl-5-phenoxyaniline Red.2-methoxy-5- Claret.

phenylmercapto-aniline. 2,6-dichloro-4-nitranilineZ-methoxy-5-phenoxyauilino, Brown.

1 part of the dyestulf of the formula O CaH is ground wet with 2 partsof a 50% aqueous solution of the sodium salt of dinaphthylmethanedisulphonic acid and dried.

The dyestutf preparation so obtained is mixed with 40 parts of a aqueoussolution sodium N-benzyl-,u heptadecyl-benzirnidazol-disulfonate andthen 4 parts of a 40% acetic acid solution are added. A dyebath of 4,000parts is prepared by dilution with Water.

100 parts of cleansed polyester fiber material are entered into thedyebath so prepared at 50 C.. the temperature is then raised to 120 to130 C. in half an hour, and dyeing is carried out for one hour at thattemperature in a closed vessel. The material is then well rinsed. Astrong red dyeing possessing an excellent fastness to light andsublimation is obtained.

What is claimed is:

1. Linear polyester fiber dyed with a water-insoluble dyestulf of theformula in which A represents the non-fiber reactive radical of abenzene or benzothiazole nucleus, X is oxygen, sulfur or a direct bond,R is cyclohexyl, aryl or aralkyl containing up to 7 carbon atoms, R ishydrogen, methyl, ethyl, methoxy, ethoxy or the residue XR 2. Polyesterfiber according to claim 1 dyed with a water-insoluble azo dyestuif asclaimed in claim 1 of the formula in which Y and Z each represents ahydrogen, chloro, bromo, fiuoro, an alkyl or alkoxy group containing upto 2 carbon atoms and X represents an oxygen, a sulphur atom or amethylene group.

3. Polyester fiber as claimed in claim 1 dyed with a dyestuif, wherein Ais the non-fiber reactive radical of a substituted benzene orbenzothiazole component.

4. Polyester fiber as claimed in claim 1 dyed with a dyestutf of theformula in which Y represents hydrogen, bromine, chlorine, methyl,methoxy, nitro. cyano, carbalkoxy containing up to 7 carbon atoms, oralkylsulphonyl containing up to 2 carbon atoms, Z represents hydrogen,cyano, trifluoromethyl, bromine, chlorine, alkyl containing up to 2carbon atoms, cyano and trifluoromethyl, Y and Z each represents ahydrogen, chloro, bromo, fiuoro, an alkyl or alkoxy group containing upto 2 carbon atoms and X represents an oxygen, a sulphur atom or amethylene group.

5. Polyester fiber according to claim 1 dyed with a compound of theformula O CoH 7. Polyester fiber according to claim 1 dyed with adyestutf of the formula 8. Polyester fiber according to claim 1 dyedwith a dyestuff of the formula OCH;

9. Polyester fiber according to claim 1 dyed with the dyestuff of theformula N (I) C Ha I l B 1' C all;

9 10 10. Polyester fiber according to claim 1 dyed with the 2,216,44610/1940 McNally et a1 260-205X dyestuif of the formula 3,081,295 3/ 1963Sterling 260205 0N 3,280,101 10/1966 Straley et a1. 260158 v FOREIGNPATENTS OzN- N=N Mn 5 363,108 8/1962 Swltzerland 260-158 0 H S GEORGE F.LESMES, Primary Examiner References cued P. C. IVES, Assistant ExaminerUNITED STATES PATENTS 10 US. Cl. X.R. 2,153,018 4/1939 Heyna et a1260-205X 2,191,040 2/1940 McNally et a1 260-206X 8179; 260-158, 205,206. 207. 207.1

2.204,607 6/1940 McNally et a1 260-206

